EP2827438A1 - Électrolyte non aqueux pour une batterie métal-air comprenant un solvant de dinitrile et batterie métal-air comprenant cet électrolyte - Google Patents

Électrolyte non aqueux pour une batterie métal-air comprenant un solvant de dinitrile et batterie métal-air comprenant cet électrolyte Download PDF

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Publication number
EP2827438A1
EP2827438A1 EP13176896.2A EP13176896A EP2827438A1 EP 2827438 A1 EP2827438 A1 EP 2827438A1 EP 13176896 A EP13176896 A EP 13176896A EP 2827438 A1 EP2827438 A1 EP 2827438A1
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EP
European Patent Office
Prior art keywords
metal
lithium
air
electrolyte
air battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP13176896.2A
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German (de)
English (en)
Inventor
Mario Dr. Marinaro
Margret Dr. Wohlfahrt-Mehrens
Ludwig Dr. Jörissen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zentrum fuer Sonnenenergie und Wasserstoff Forschung Baden Wuerttemberg
Original Assignee
Zentrum fuer Sonnenenergie und Wasserstoff Forschung Baden Wuerttemberg
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Priority to EP13176896.2A priority Critical patent/EP2827438A1/fr
Publication of EP2827438A1 publication Critical patent/EP2827438A1/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to non-aqueous electrolytes for metal-air batteries. More specifically the present invention is related to the use of a non-aqueous electrolyte solution comprised of at least a dinitrile-based solvent and an alkali metal salt that assure ionic conductivity between the electrodes of the electrochemical cell. The invention also relates to metal-air batteries using said non-aqueous electrolytes.
  • the aprotic electrolyte rechargeable lithium-air batteries offer one of the highest specific energies among electrochemical energy storage devices. Lithium-air batteries have indeed the potential to overtake the battery technology in use today. Increasing efforts are therefore focused on the development of such kind of battery technology.
  • lithium-air batteries consist in an air cathode, a lithium metal anode, a separator and an electrolyte solution.
  • the possible reactions that take place during the charge and the discharge process are listed below:
  • Rechargeability is the most difficult obstacle to overcome when a renewable energy storage system device is realized.
  • the oxidation of the reduction products is thermodynamically unfavourable and suffers from poor kinetics.
  • the first attempt of a lithium-air battery was developed using a lithium metal anode, a porous carbon cathode and a gel-polymer electrolyte 1 . Without the use of any catalysts the oxidation takes place near 4 V vs. Li + /Li, giving rise to a large hysteresis. Such hysteresis was reduced by employing a cobalt phtalocyanine-based oxidation catalyst, which also improved the charge/discharge efficiency. More recently manganese oxide (MnO 2 ) has been employed as catalyst even if the charge voltage is almost unaffected by the presence of this compound 2 .
  • MnO 2 manganese oxide
  • N,N-dialkylamides such as dimethylformamide and acetamide
  • lactams such as N-methylpyrrolidone
  • WO 2007/062220 A2 describes a non-aqueous alkali metal/oxygen battery cell comprising a protective anode, a protective membrane architecture, a cathode compartment comprising an oxygen electrode, a non-aqueous electrolyte and molecular oxygen, wherein the non-aqueous electrolyte solvent may include nitriles, amides, amines, organosulfur solvents or organophosphorous solvents.
  • Another object of the invention is to provide a stable electrolyte system with respect to anode, cathode and separator materials usually used in metal- and lithium-air batteries.
  • the present invention wants to provide a non-aqueous electrolyte that is resistant to the oxygen reduction products, such as lithium peroxide and lithium oxide, that form during the discharge process of a typical primary or secondary metal- and lithium-air battery.
  • the electrolyte system presented in this invention is thought to be used in primary and secondary lithium-air and metal-air cells.
  • the present invention provides a non-aqueous electrolyte for a metal-air battery comprising a dinitrile solvent and an alkali metal salt.
  • the subject-matter of the present invention relates to a metal-air battery comprising
  • the non-aqueous electrolyte of the invention shows stability during the oxygen reduction reaction as well as during oxygen evolution reaction. With such an electrolyte, a high degree of reversibility and cyclability is obtained.
  • the non-aqueous electrolyte of the present invention is based on a dinitrile solvent and an alkali metal salt.
  • the dinitrile is represented by the general formula (1) wherein n is an integer from 1 to 6, preferably 2 to 5, more preferably 3 or 4, and most preferably 4 (adiponitrile).
  • n is an integer from 1 to 6, preferably 2 to 5, more preferably 3 or 4, and most preferably 4 (adiponitrile).
  • adiponitrile The physical/chemical properties of adiponitrile are listed in Table 1.
  • dinitriles adiponitrile and glutaronitrile for instance, exhibit an electrochemical stability window of about 6 V vs. Li + /Li.
  • dinitriles show good thermal (high boiling point and flash point) and chemical/physical properties (high dielectric constant, low viscosity and low vapour pressure).
  • the alkali metal salt is preferably a lithium salt. More preferably, the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiSO 3 CF 3 , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiB(C 2 O 4 ) 2 , and LiPF 3 (C 2 F 5 ) 3 , preferably selected from LiN(CF 3 SO 2 ) 2 and LiBF 4 , most preferably is LiN(CF 3 SO 2 ) 2 .
  • LiN(CF 3 SO 2 ) 2 i.e. lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and LiBF 4 have the chemical structures reported below:
  • the metal anode may also comprise a metal intercalation compound.
  • the metal-air battery is a lithium-air battery comprising a lithium metal anode as the metal anode.
  • the air cathode may preferably comprise porous carbon.
  • the air cathode comprises a catalyst material to improve the cathode performance
  • the catalyst material is preferably a metal catalyst material comprising manganese, cobalt, ruthenium, platinum, silver or mixtures thereof.
  • Adiponitrile has been dried over molecular sieve (4 ⁇ ) and stored in an Argon filled glove-box where the oxygen and water content have been kept below 0.1 ppm.
  • the water content in the solvent after the drying process has been determined through coulometric Karl-Fischer titration. The water content was always below 10 ppm.
  • the non-aqueous electrolyte has been prepared in an Argon filled glove box by dissolving 0.1 mol of the alkali metal salt (LiTFSI) in 1 litre of solvent. Depending on the chemical nature of the salt, heat has been applied in order to facilitate the fully dissolution.
  • LiTFSI alkali metal salt
  • the viscosity and the density of the non-aqueous electrolyte system prepared as described in Example 1 have been determined in the temperature range 0 ⁇ T(°C ) ⁇ 40. The obtained values are given in Table 2. The viscosity and the density have been measured using a SVM 3000 Stabinger Viscometer by Anton Paar. Table 2 Temp.
  • the conductivity of the electrolyte solution prepared following the procedure reported in the Example 1 has been determined as function of the temperature. Starting from 25°C the temperature was first increased and then decreased down to 0°C. The conductivity experiments were carried out in an Argon filled glove-box where the oxygen and water content were below 0.1 ppm. The obtained results are given in Table 3. The conductivity has been determined using a microcell HC by rhd-instruments apparatus. Table 3 Temp. Conductivity [°C] [mS/cm] 0 °C 0,343 10 °C 0,494 20 °C 0,62 25 °C 0,741 30 °C 0,848 40 °C 1,05
  • Cyclic voltammetry was used to investigate the electrochemical properties of the non-aqueous electrolyte solution LiTFSI 0.1 M in Adiponitrile prepared as described in Example 1.
  • the cyclic voltammograms were collected using an electrochemical cell in which glassy carbon (3 mm in diameter) acted as the working electrode, platinum as the counter electrode and metallic lithium as the reference electrode.
  • the cyclic voltammograms were collected with a sweep rate of 100 mV s -1 .
  • FIG.1 depicts a graph indicating two separate cyclic voltammograms overlaid.
  • the dotted cyclic voltammogram refers to the Argon background collected in the potential window of 1-5 V vs. Li + /Li.
  • the electrolyte solution of the present invention appears to be stable in the investigated potential window. Oxygen was subsequently bubbled in the electrolyte for 30 minutes in order to have an oxygen-saturated environment.
  • ) are separated by 195mV indicating a multi-electrons reduction reaction.
  • FIG. 2A and FIG. 2B depict graphs showing the anodic and cathodic peak potential variations with the sweep rate.
  • the experiment was carried out using an electrochemical cell with a glassy carbon working electrode, platinum foil as counter electrode and lithium foil as the reference electrode.
  • the increasing of the sweep rate reflects in the voltammograms a shift of the cathodic and anodic peaks towards more negative and more positive potentials, respectively. Regardless to the sweep rate and hence for all the cyclic voltammograms, the ratio Q a /Q c has been found close to the unity suggesting a reversible electrochemical reaction.
  • Example 5 The obtained experimental data given in Example 5 were used to compute a typical plot, shown in FIG. 3 , which illustrates the relationship between the cathodic peak current (I pc ) and the square root of the sweep rate. It can be seen that there is an obvious linear relationship among the experimental data, suggesting a diffusion controlled electrochemical process. Indeed, the computed linear fit shows a nice correlation coefficient (
  • FIG. 4 depicts a graph indicating the cyclability of the non-aqueous electrolyte solution LiTFSI 0.1 M in Adiponitrile obtained utilizing an electrochemical cell where glassy carbon acted as the working electrode, platinum as the counter electrode and metallic lithium as the reference.
  • oxygen was bubbled in the electrolyte solution in order to have an oxygen saturated environment.
  • the three overlapped cyclic voltammograms show that in the investigated potential window of 2-4.5 V vs. Li + /Li, the electrolyte under investigation provides full stability and rechargeability.
  • the ratio Q a /Q c determined from the area under the oxidation (I pa ) and reduction (I pc ) peaks is close to the unity indicating a high degree of reversibility of the electrochemical reaction.
  • FIG. 5 illustrates a typical galvanostatic curve collected with a current density of 50 mA (g of carbon)-1 and with capacity limitation of 500 mAh (g of carbon)-1.
  • the galvanostatic plot features a flat discharge plateau consistent with the reduction of oxygen. Charging the cell translates into an increase of the cell voltage that approaches the end of the charge slightly above 4 V vs. Li.
  • FIG. 6 shows a comparison between the X-Ray diffraction patterns of a pristine and a discharged electrode.
  • the diffractogram clearly shows that the discharge leads to the formation of crystalline Li2O2 as desired products, whereas no other crystalline phases can be detected.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
EP13176896.2A 2013-07-17 2013-07-17 Électrolyte non aqueux pour une batterie métal-air comprenant un solvant de dinitrile et batterie métal-air comprenant cet électrolyte Withdrawn EP2827438A1 (fr)

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EP13176896.2A EP2827438A1 (fr) 2013-07-17 2013-07-17 Électrolyte non aqueux pour une batterie métal-air comprenant un solvant de dinitrile et batterie métal-air comprenant cet électrolyte

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EP13176896.2A EP2827438A1 (fr) 2013-07-17 2013-07-17 Électrolyte non aqueux pour une batterie métal-air comprenant un solvant de dinitrile et batterie métal-air comprenant cet électrolyte

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3404761A1 (fr) * 2017-05-16 2018-11-21 Ricoh Company, Limited Élément de stockage d'électricité à électrolyte non aqueux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070117007A1 (en) * 2005-11-23 2007-05-24 Polyplus Battery Company Li/air non-aqueous batteries
WO2008138132A1 (fr) * 2007-05-15 2008-11-20 National Research Council Of Cananda Électrolytes liquides à base de dinitrile
WO2012146525A1 (fr) * 2011-04-26 2012-11-01 Solvay Sa Élément de batterie lithium-air

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070117007A1 (en) * 2005-11-23 2007-05-24 Polyplus Battery Company Li/air non-aqueous batteries
WO2007062220A2 (fr) 2005-11-23 2007-05-31 Polyplus Battery Company Batteries non aqueuses li/air
WO2008138132A1 (fr) * 2007-05-15 2008-11-20 National Research Council Of Cananda Électrolytes liquides à base de dinitrile
WO2012146525A1 (fr) * 2011-04-26 2012-11-01 Solvay Sa Élément de batterie lithium-air

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ABRAHAM, K. M.; JIANG, Z., J. ELECTROCHEM. SOC, vol. 143, 1996, pages 1 - 5
DÉBART, A; PATERSON, ALLAN J.; BAO, J.; BRUCE, PETER G., ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 47, 2008, pages 4521 - 4524
FREUNBERGER, S. A.; CHEN, Y.; PENG, Z.; GRIFFIN, J. M.; HARDWICK, L. J.; BARDE, F.; NOVÁK, P.; BRUCE, P., J. AM. CHEM. SOC., vol. 133, 2011, pages 8040 - 8047
JAKE CHRISTENSEN ET AL: "A Critical Review of Li/Air Batteries", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 159, no. 2, 29 December 2011 (2011-12-29), pages R1, XP055038894, ISSN: 0013-4651, DOI: 10.1149/2.086202jes *
LINDEN, D.; REDDY, T.: "Handbook of Batteries", 2001, MCGRAW-HILL
READ, J., JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 149, 2002, pages A1190 - A1195
S. A. FREUNBERGER; Y. CHEN; N. E. DREWETT; L. J. HARDWICK; F. BARDÉ; P. G. BRUCE, ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 8609 - 8613
V. S. BRYANTSEV ET AL: "The Identification of Stable Solvents for Nonaqueous Rechargeable Li-Air Batteries", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 160, no. 1, 21 November 2012 (2012-11-21), pages A160 - A171, XP055050304, ISSN: 0013-4651, DOI: 10.1149/2.027302jes *
Y. CHEN; S. A. FREUNBERGER; Z. PENG; F. BARDÉ; P. G. BRUCE, J. AM. CHEM. SOC., vol. 134, 2012, pages 7952 - 7957

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3404761A1 (fr) * 2017-05-16 2018-11-21 Ricoh Company, Limited Élément de stockage d'électricité à électrolyte non aqueux

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